Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

Reutilização de baterias automotivas como fonte alternativa de energia.

Atualmente um dos principais objetivos na área de pesquisa tecnológica é o desenvolvimento de soluções em favor do Meio Ambiente. Este trabalho tem por objetivo demonstrar a reutilização e consequentemente o aumento da vida útil de uma bateria Chumbo-Ácido, comumente instaladas em veículos automóveis, bem como beneficiar locais e usuários remotos onde o investimento na instalação de linhas de transmissão se torna inviável geográfica e economicamente, utilizando a luz solar como fonte de energia. No entanto a parte mais suscetível a falhas são as próprias baterias, justamente pela vida útil delas serem pequenas (em torno de 3 anos para a bateria automotiva) em comparação com o restante do sistema. Considerando uma unidade que já foi usada anteriormente, a possibilidade de falhas é ainda maior. A fim de diagnosticar e evitar que uma simples bateria possa prejudicar o funcionamento do sistema como um todo, o projeto considera a geração de energia elétrica por células fotovoltaicas e também contempla um sistema microcontrolado para leitura de dados utilizando o microcontrolador ATmega/Arduino, leitura de corrente por sensores de efeito hall da Allegro Systems, relés nas baterias para abertura e fechamento delas no circuito e um sistema de alerta para o usuário final de qual bateria está em falha e que precisa ser reparada e/ou trocada. Esse projeto foi montado na Ilha dos Arvoredos SP, distante da costa continental em aproximadamente 2,0km. Foram instaladas células solares e um banco de baterias, a fim de estudar o comportamento das baterias. O programa pôde diagnosticar e isolar uma das baterias que estava apresentando defeito, a fim de se evitar que a mesma viesse a prejudicar o sistema como um todo. Por conta da dificuldade de locomoção imposta pela geografia, foi escolhido o cartão SD para o armazenamento dos dados obtidos pelo Arduino. Posteriormente os dados foram compilados e analisados. A partir dos resultados apresentados podemos concluir que é possível usar baterias novas e baterias usadas em um mesmo sistema, de tal forma que se alguma das baterias apresentar uma falha o sistema por si só isolará a unidade.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Mesoporous materials for clean energy technologies

Alternative energy technologies are greatly hindered by significant limitations in materials science. From low activity to poor stability, and from mineral scarcity to high cost, the current materials are not able to cope with the significant challenges of clean energy technologies. However, recent advances in the preparation of nanomaterials, porous solids, and nanostructured solids are providing hope in the race for a better, cleaner energy production. The present contribution critically reviews the development and role of mesoporosity in a wide range of technologies, as this provides for critical improvements in accessibility, the dispersion of the active phase and a higher surface area. Relevant examples of the development of mesoporosity by a wide range of techniques are provided, including the preparation of hierarchical structures with pore systems in different scale ranges. Mesoporosity plays a significant role in catalysis, especially in the most challenging processes where bulky molecules, like those obtained from biomass or highly unreactive species, such as CO2 should be transformed into most valuable products. Furthermore, mesoporous materials also play a significant role as electrodes in fuel and solar cells and in thermoelectric devices, technologies which are benefiting from improved accessibility and a better dispersion of materials with controlled porosity.

The Modelling of Photovoltaic, Solar Thermal, and Photovoltaic/Thermal Domestic Hot Water Systems

Solar heating of potable water has traditionally been accomplished through the use of solar thermal (ST) collectors. With the recent increases in availability and lower cost of photovoltaic (PV) panels, the potential of coupling PV solar arrays to electrically heated domestic hot water (DHW) tanks has been considered. Additionally, innovations in the SDHW industry have led to the creation of photovoltaic/thermal (PV/T) collectors, which heat water using both electrical and thermal energy. The current work compared the performance and cost-effectiveness of a traditional solar thermal (ST) DHW system to PV-solar-electric DHW systems and a PV/T DHW system. To accomplish this, a detailed TRNSYS model of the solar hot water systems was created and annual simulations were performed for 250 L/day and 325 L/day loads in Toronto, Vancouver, Montreal, Halifax, and Calgary. It was shown that when considering thermal performance, PV-DHW systems were not competitive when compared to ST-DHW and PVT-DHW systems. As an example, for Toronto the simulated annual solar fractions of PV-DHW systems were approximately 30%, while the ST-DHW and PVT-DHW systems achieved 65% and 71% respectively. With current manufacturing and system costs, the PV-DHW system was the most cost-effective system for domestic purposes. The capital cost of the PV-DHW systems were approximately $1,923-$2,178 depending on the system configuration, and the ST-DHW and PVT system were estimated to have a capital cost of $2,288 and $2,373 respectively. Although the capital cost of the PVT-DHW system was higher than the other systems, a Present Worth analysis for a 20-year period showed that for a 250 L/day load in Toronto the Present Worth of the PV/T system was approximately $4,597, with PV-DHW systems costing approximately $7,683-$7,816 and the ST-DHW system costing $5,238.

Estudo de camadas anti-reflectoras para células solares

Trabalho de projecto de mestrado, Engenharia da Energia e Ambiente, Universidade de Lisboa, Faculdade de Ciências, 2016

Sequential purification and crystal growth for the production of low cost silicon substrates : quarterly technical progress report no. 1, September 15-December 31, 1979 /

"February 1980."

Sequential purification and crystal growth for the production of low cost silicon substrates : annual report, September 15, 1979-September 14, 1980 /

"Work Performed Under Contract No. AC02-77CH00178."

Sequential purification and crystal growth for the production of low cost silicon substrates : quarterly technical progress report no. 3, April 1-June 30, 1980 /

"August 1980."

Photoelectronic properties of zinc phosphide crystals, films and heterojunctions : quarterly progress report no. 6 for the period July 1 - September 30, 1980 /

The purpose of this research program is to investigate the photoelectronic properties of zinc phosphide (Zn₃P₂ in single crystal form, in thin-film form, and in heterojunctions in which Zn₃P₂ forms one of the elements. This research will be directed toward understanding the role of crystalline defects and impurities in Zn₃P₂, the nature of the electronic charge transport in single crystal and thin-film material, and the properties of photovoltaic heterojunctions involving Zn₃P₂. The scope of the program extends from basic investigations of materials properties on single crystals to the preparation and characterization of all-thin-film heterojunction divices. One of the principal motivations behind this research program is the realization that Zn₃P₂ is a relatively uninvestigated yet ideal component for photovoltaic heterojunction use in solar energy conversion. The proposed program will concentrate on the basic materials problems involved with Zn₃P₂, providing the kind of information needed for other more developmental programs directed toward actual practical cells.

Materials studies related to the Cu₂S/ZnCdS heterojunction : first quarterly report for period March 15 - June 15, 1980 /

"Work Performed Under Contract No. AC02-77CH00178."

The growth of silicon sheets for photovoltaic applications /

The status of silicon sheet development for photovoltaic applications is critically reviewed. Silicon sheet growth processes are classified according to their linear growth rates. The "fast" growth processes, which include edge-defined film-fed growth, silicon on ceramic, dendritic-web growth, and ribbon-to-ribbon growth, are comparatively ranked subject to criteria involving growth stability, sheet productivity, impurity effects, crystallinity, and solar cell results. The status of more rapid silicon ribbon growth techniques, such as horizontal ribbon growth and melt quenching, is also reviewed. The emphasis of the discussions is on examining the viability of these sheet materials as solar cell substrates for low-cost silicon photovoltaic systems.

A PbS quantum-cube: conducting polymer composite for photovoltaic applications

We have developed a new non-polar synthesis for lead sulfide (PbS) quantum-cubes in the conjugated polymer poly-2-methoxy, 5-(2-ethyl-hexyloxy-p-phenylenevinylene) MEH-PPV. The conducting polymer acts to template and control the quantum-cube growth. Transmission electron microscopy of the composites has shown a bimodal distribution of cube sizes between 5 and 15 nm is produced with broad optical absorption from 300 to 650 nm. Photoluminescence suggests electronic coupling between the cubes and the conducting polymer matrix. The synthesis and initial characterization are presented in this paper. (C) 2003 Elsevier B.V. All rights reserved.

Formation of mesostructured titania thin films using iospropoxide precursors

Mesostructured titania thin films were prepared by an evaporation-induced self-assembly process. The highly acidic sot precursors contained titanium(IV) tetraisopropoxide (TTIP) as a titanium source, a tri-block copolymer Pluronic P123 as a template, and acetylacetonate and HCl as hydrolysis inhibitors. Characteristics of the resultant titania thin films were studied using X-ray diffraction (XRD) analysis, N-2-adsorption/desorption analysis, and transmission electron microscopy (TEM). XRD and TEM investigations on the as-synthesised films revealed the appearance of cubic-like, pseudohexagonal, and lamellar mesophases; depending on the amount of water in the sols of film precursors. Template removal by a calcination process yields high surface area (320-360 m(2)/g) mesoporous materials with crystalline anatase frameworks. Water content also influences the degree of anatase crystallinity of the calcined films. Higher water content resulted in improved anatase crystallinity. These nanostructured materials are of interest for photocatalysts, pbotoelectrochemical solar cells and other photonic devices. (C) 2003 Elsevier B.V. All rights reserved.